CN109456841B

CN109456841B - Color-protecting liquid fabric detergent composition

Info

Publication number: CN109456841B
Application number: CN201811503330.7A
Authority: CN
Inventors: 马骏; 邱振名; 李东华; 黄亮; 罗勇; 张利萍
Original assignee: Guangzhou Liby Enterprise Group Co Ltd
Current assignee: Guangzhou Liby Enterprise Group Co Ltd
Priority date: 2018-12-10
Filing date: 2018-12-10
Publication date: 2021-05-18
Anticipated expiration: 2038-12-10
Also published as: CN109456841A

Abstract

The invention discloses a color-protecting liquid fabric detergent composition, and relates to the technical field of daily chemical industry. The composition comprises: 5-70 parts of a surfactant; 0.1-5 parts of modified polyethyleneimine; 0.01 to 1 part of cationic polymer and 0.1 to 30 parts of additive. The color-protecting liquid fabric detergent composition provided by the invention can simultaneously improve the cross color prevention performance and the color loss prevention performance of the liquid fabric detergent by compounding the modified polyethyleneimine and the cationic polymer; the appearance of the fabric is not obviously influenced; has good stability and decontamination performance.

Description

Color-protecting liquid fabric detergent composition

Technical Field

The invention relates to the technical field of daily-use chemical industry, in particular to a color-protecting liquid fabric detergent composition.

Background

Fabric washing products are becoming more and more diverse, and consumers are more concerned about performance other than detergency, especially about protection of fabric color, in addition to differences in detergency when selecting products.

The process of washing the fabric needs to go through several stages of soaking, washing and rinsing. Throughout the process, dark fabrics inevitably come out of the dye and cross-stain between the various fabrics being washed. At this time, the discoloration of the light colored fabric subjected to the cross dyeing is generally more obvious, and therefore, developers in the field have focused more on the discoloration problem of the light colored fabric and provided some solutions. In the existing solution for the color change of light-colored fabrics, polymers with the color cross-dyeing prevention function are mainly introduced, and the polymers can adsorb free dye molecules in the washing process, so that the occurrence of cross-dyeing is blocked. This solution does work well to protect light fabrics, but it has been found in different formulations that such polymers often significantly accentuate the removal of coloured fabric dyes.

Some solutions also appear at present in the color protection of dark fabrics. The fixation polymer in the printing and dyeing industry is mainly directly introduced into a liquid detergent so as to relieve decoloration, but the conventional fixation polymer and the detergent are difficult to stably compound and can influence the final washing effect. Moreover, if the dye fixing polymer is improperly used, excessive adsorption of the dye fixing polymer on the surface of the fabric can cause discoloration of the fabric, which leads to undesirable associations of fabric damage, harmful residues and the like for consumers. In addition, the addition of cellulase to a detergent is also one of the treatment methods, and the cellulase is used for removing the decolorized damaged fibers on the surface of the fabric, so that the fabric can restore the original color to a certain extent. The method has obvious effect, but can affect the flexibility of the fabric, and is not suitable for long-term use.

Disclosure of Invention

The invention aims to solve the technical problem that under the premise of ensuring stability and detergency, the deep and light fabrics can be protected from cross dyeing and decoloration by jointly washing, and the detergent composition with good color protection performance is provided.

In order to solve the above problems, the present invention provides the following technical solutions:

a color-protecting liquid fabric detergent composition comprises the following components in parts by weight:

5-70 parts of a surfactant;

0.1-5 parts of modified polyethyleneimine;

0.01-1 part of cationic polymer;

0.1-30 parts of an additive;

wherein the surfactant system comprises at least one of an anionic surfactant, a cationic surfactant, a nonionic surfactant and an amphoteric surfactant;

the cationic polymer has

And wherein

Is a cation structural unit, wherein a and b are positive integers; structural units in the cationic polymer

Selected from:

at least one of (1).

The further technical scheme is that the ratio of the modified polyethyleneimine to the cationic polymer is 30:1 to 3:1 in parts by weight

The further technical scheme is that the modified polyethyleneimine is ethoxy and/or propoxy modified polyethyleneimine.

The further technical scheme is that the modified polyethyleneimine is ethoxy modified polyethyleneimine.

The further technical scheme is that the weight average molecular weight of a main chain in the modified polyethyleneimine is 300-8000.

The further technical scheme is that the average ethoxylation degree of the modified polyethyleneimine is 2 to 50.

The further technical proposal is that the weight of the cationic structural unit in the cationic polymer accounts for 15 to 50 percent of the total weight of the cationic polymer.

The further technical proposal is that the cationic structural unit in the cationic polymer

Selected from compounds corresponding to the following general formula (1):

wherein R is¹Is selected from C_nH_2n+1、C_mH_2m-1、(CH₂CH₂O)_vH. At least one of phenyl or naphthyl, n is 0-4, m is 5-8, v is 1-3;

R²is selected from C_nH_2n+1、C_mH_2m-1、(CH₂CH₂O)_vH. At least one of phenyl or naphthyl, n is 0-4, m is 5-8, v is 1-3;

x is selected from OH, Cl, Br or CH₃OSO₃At least one of (1).

Selected from compounds corresponding to the following general formula (2):

wherein Y is selected from O or NR³At least one of;

z is selected from C_nH_2n、C_mH_2m-2At least one of phenyl or naphthyl, n is 1-6, m is 5-8;

R³is selected from H or CH₃；

R⁴Is selected from C_nH_2n+1、C_mH_2m-1、(CH₂CH₂O)_vH. At least one of phenyl or naphthyl, n is 0-4, m is 5-8, v is 1-3;

R⁵is selected from C_nH_2n+1、C_mH_2m-1、(CH₂CH₂O)_vH. At least one of phenyl or naphthyl, n is 0-4, m is 5-8, v is 1-3;

R⁶is selected from C_nH_2n+1、C_mH_2m-1、(CH₂CH₂O)_vH. At least one of phenyl or naphthyl, n is 0-4, m is 5-8, v is 1-3;

x is selected from OH, Cl, Br or CH₃OSO₃At least one of (1).

The technical scheme is that the additive comprises at least one of an enzyme preparation, an alkaline agent, a viscosity regulator, a cosolvent, a pH stabilizer, a preservative, a coloring agent, a washing assistant, a color stabilizer and essence.

Compared with the prior art, the invention can achieve the following technical effects:

according to the color-protecting liquid fabric detergent composition, the cross-color prevention performance and the anti-fading performance of the liquid fabric detergent can be improved simultaneously by compounding the modified polyethyleneimine and the cationic polymer;

2. in a suitable ratio range, the liquid detergent composition containing the modified polyethyleneimine and the cationic polymer does not have a significant effect on the appearance of fabrics while providing good anti-cross-color and anti-fading functions;

3. the liquid detergent composition containing polyethyleneimine and cationic polymer is matched with each other through proper proportion of the components to generate a synergistic effect, so that the liquid detergent composition not only can provide good color protection performance, but also has good stability and stain removal performance, can give consideration to dark and light-colored clothes at the same time, and greatly facilitates a washing procedure.

Detailed Description

The features, benefits and advantages of the present invention will become apparent to those skilled in the art from a reading of the present disclosure. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

All percentages, parts and ratios are based on the total weight of the composition of the present invention, unless otherwise specified. All weights as they pertain to listed ingredients are assigned to levels of active material and, therefore, do not include solvents or by-products that may be included in commercially available materials, unless otherwise specified. The term "weight content" herein may be represented by the symbol "%".

All molecular weights herein are weight average molecular weights expressed in daltons, unless otherwise indicated.

All formulations and tests herein occur at 25 ℃ environment, unless otherwise indicated.

The use of "including," "comprising," "containing," "having," or other variations thereof herein, is meant to encompass the non-exclusive inclusion, as such terms are not to be construed. The term "comprising" means that other steps and ingredients can be added that do not affect the end result. The term "comprising" also includes the terms "consisting of …" and "consisting essentially of …". The compositions and methods/processes of the present invention can comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein.

It is also to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the invention. As used in the description of embodiments of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

Modified polyethyleneimine

The color-protecting liquid fabric detergent composition provided by the embodiment of the invention contains 0.1-5 parts by weight of modified polyethyleneimine.

In certain embodiments, the modified polyethyleneimine is an ethoxy and/or propoxy modified polyethyleneimine.

For example, in one embodiment, the modified polyethyleneimine is an ethoxy modified polyethyleneimine, a propoxy modified polyethyleneimine or a polyethyleneimine modified with both ethoxy and propoxy groups.

In one embodiment, the modified polyethyleneimine is an ethoxy modified polyethyleneimine.

In certain embodiments, the weight average molecular weight of the polyethyleneimine backbone in the ethoxy modified polyethyleneimine is from 300 to 8000.

In one embodiment, the average degree of ethoxylation in the ethoxy-modified polyethyleneimine is from 2 to 50, preferably from 5 to 40, more preferably from 10 to 30.

Cationic polymers

In particular embodiments, cationic polymers that may be generally employed in liquid detergents include cationically modified starches, celluloses, silicones, polyamines, polyamides or cationic homopolymers and copolymers formed by polymerization of cationic monomers.

The color-protecting liquid fabric detergent composition provided by the embodiment of the invention contains 0.01-1 part by weight of cationic polymer; the cationic polymer has

And wherein

Is a cation structural unit, wherein a and b are positive integers.

In one embodiment, the cationic polymer has a weight of cationic structural units in the range of 15% to 50% of the total weight of the cationic polymer.

In one embodiment, the weight average molecular weight in the cationic polymer is 1.0 × 10⁴To 1.5X 10⁵。

In one embodiment, the cationic structural units in the cationic polymer

Selected from compounds corresponding to the following general formula (1):

x is selected from OH, Cl, Br or CH₃OSO₃At least one of (1).

In one embodiment, R¹Is CH₃，R²Is CH₃。

In one embodiment, the cationic structural units in the cationic polymer

Selected from compounds corresponding to the following general formula (2):

wherein Y is selected from O or NR³At least one of;

R³is selected from H or CH₃；

x is selected from OH, Cl, Br or CH₃OSO₃At least one of (1).

In one embodiment, Z has the structure-CH₂CH₂-or-CH (CH)₃)CH₂-。

In one embodiment, R⁴Is CH₃，R⁵Is CH₃，R⁶Is CH₃。

In one embodiment, the structural units in the cationic polymer

At least one selected from the following structures:

in one embodiment, the structural units in the cationic polymer

Is composed of

Surfactant system

The liquid detergent composition according to the present invention contains 5 to 70 parts by weight of a surfactant. Suitable surfactant systems include, but are not limited to: one of anionic surfactant, nonionic surfactant, amphoteric surfactant and their mixture.

Anionic surfactants

The total weight of the mixture of anionic surfactants is from 0% to 45% of the total weight of the liquid detergent composition.

The anionic surfactant is selected from one or more of sulfonate surfactant, carboxylate surfactant and sulfate surfactant; preferably one or more of alkyl benzene sulfonate, alkyl sulfate of C8-C18, ethoxylated fatty alcohol sulfate of C8-C18, alpha-olefin sulfonate, fatty acid alkyl ester sulfonate and ethoxylated fatty alcohol ether carboxylate.

In some embodiments, the mixture of anionic surfactants preferably contains alkyl benzene sulfonates and derivatives thereof. The alkylbenzene sulfonate satisfies the following general formula (3):

in the general formula (3), R¹Is an alkyl group having 6 to 24 carbon atoms, M⁺Is a cation. R¹May be a straight-chain alkyl group or a branched-chain alkyl group; it may be a saturated alkyl group or an alkyl group having one or more unsaturated double bonds. More preferably R¹Is a straight chain alkyl group having a carbon number of 8 to 18.

In some embodiments, the mixture of anionic surfactants contains ethoxylated fatty alcohol sulfates. Ethoxylated fatty alcohol sulfates are derivatives of ethoxylated fatty alcohols having the following general formula (4):

in the general formula (4), R¹Is an alkyl group having 6 to 24 carbon atoms; x is 0.5 to 30; wherein M is⁺Is a cation. R¹May be a straight-chain alkyl group or a branched-chain alkyl group; it may be a saturated alkyl group or an alkyl group having one or more unsaturated double bonds. Preferably R¹Is a straight chain alkyl group having a carbon number of 8 to 18. x represents an average degree of ethoxylation of from 0.5 to 30, preferably from 0.5 to 10, more preferably from 0.5 to 3.

In some embodiments, an alpha-olefin sulfonate is included having the following general formula (5):

in the general formula (5), a is 0 to 2, wherein M⁺Is a cation, R¹Is an alkyl group having 6 to 24 carbon atoms, preferably R¹Is an alkyl group having 8 to 18 carbon atoms.

The anionic surfactant may also include one or more mixtures of sodium alkyl disulfonates or derivatives thereof, preferably sodium alkyl diphenyl ether disulfonates, for example, in one embodiment the anionic surfactant is sodium dodecyl diphenyl ether disulfonate.

The anionic surfactant may also include fatty acid alkyl ester sulfate, preferably fatty acid Methyl Ester Sulfate (MES), preferably fatty acid carbon number of 8 to 18.

The anionic surfactant may also include a sulfosuccinate, preferably fatty alcohol polyoxyethylene ether sulfosuccinic acid monoester disodium salt, the fatty alcohol preferably having 8 to 18 carbon atoms and an average degree of ethoxylation of preferably 2.0.

Nonionic surfactant

In a specific embodiment, the total weight of the mixture of nonionic surfactants is from 5% to 65% of the total weight of the liquid detergent composition.

The nonionic surfactant is selected from one or more of fatty alcohol alkoxylates, alkyl polyglycosides, fatty acid alkoxylates, fatty acid ethoxylates, fatty acid alkylolamides, and ethoxylated sorbitan esters.

In some embodiments, the nonionic surfactant mixture preferably contains a fatty alcohol alkoxylate having the following general formula (6):

in the general formula (6), n is 6 to 24; x is 0.5 to 30 and y is 0 to 10.

It should be noted that the fatty alcohol alkoxylate is a product of ring-opening polymerization of a fatty alcohol and an alkylene oxide in the presence of an alkaline catalyst, and thus is a mixture. The fatty alcohol includes a straight chain alcohol or a branched chain isomeric alcohol. Alkoxy groups include ethoxy and propoxy groups. The fatty alcohol is preferably a fatty alcohol having a carbon number of 8 to 18, and the preferred alcohols include, but are not limited to, one of hexanol, octanol, decanol, 2-ethylhexanol, 3-propylheptanol, lauryl alcohol, isotridecyl alcohol, tridecyl alcohol, tetradecyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, and mixtures thereof. The average degree of ethoxylation x is preferably from 2 to 12. Preferred examples are the NEODOL series of linear fatty alcohol ethoxylates products from SHELL, the ECOSURFEH series of ethoxylated and propoxylated 2-ethylhexanols products from DOW, the Lutensol XL series of ethoxylated and propoxylated 3-propylheptanols products from BASF and the Lutensol XP series of ethoxylated 3-propylheptanols from BASF.

In some embodiments, the nonionic surfactant mixture preferably contains an alkyl polyglycoside having the following general formula (7):

in the general formula (7), n is 6 to 24, p is 1.1 to 3, and preferably n is 8 to 16. In one embodiment, alkyl polyglycosides such as the Glucopon series of alkyl glycosides from BASF are selected.

The nonionic surfactant mixture may contain fatty acid alkoxylates, preferably from ethoxylated C8 to C18 fatty acid esters, with an average degree of ethoxylation of from 2 to 10. May contain an ethoxylated alkyl sorbitan ester having an alkyl carbon number of from 6 to 18 and an average degree of ethoxylation of from 4 to 20; a suitable example is the Corda Tween series of products.

The nonionic surfactant mixture may contain fatty acid alkylolamides, the fatty acid having 6 to 24 carbon atoms, may be a linear fatty acid, may be a branched fatty acid, may be a saturated fatty acid, and may be an unsaturated fatty acid; the alkyl alcohol number is 0 to 2. Monoethanolamide, diethanolamide, isopropanolamide of fatty acids having a carbon number of 8 to 18 are preferred, a suitable example being coconut diethanolamide.

The nonionic surfactant mixture may contain fatty acid methyl ester ethoxylates of the following general formula (8):

in the general formula (8), n is 6 to 24; x is 2 to 20, preferably n is 8 to 18, x is 0.5 to 30. Preferably x is 4 to 10.

The nonionic surfactant mixture may also contain a polyether surfactant. The polyether surfactant is a polymer, a nonionic surfactant containing ethoxy and/or propoxy repeating units, suitable examples being the Pluronic series from BASF.

Additive:

enzyme preparation

One or more enzyme preparations may be included in the detergent compositions of the present invention to enhance the soil release properties of the product and to provide other benefits to fabric care. The enzyme preparation is selected from the following enzymes: proteases, alpha-amylases, cellulases, hemicellulases, phospholipases, esterases, lipases, peroxidases/oxidases, pectinases, lyases, mannanases, cutinases, reductases, xylanases, pullulanases, tannases, pentosanases, maltoglucanases, arabinases, beta-glucanases, preferably proteases. Suitable proteases include, but are not limited to, Savinase16L from Novin, Savinase Ultra16XL, SavinaseEvent 16L, Progress Uno 101L, Progress Uno 100L, Effect P150 from Dupont, preferenzP200, preferenzP300, Lavergy 104L, 104L LS from Pasteur. The enzyme preparation is present in an amount of from 0.001% to 5%, preferably from 0.01% to 2%, by weight of the total detergent composition.

Alkaline agent

In some embodiments, it is desirable to neutralize the anionic surfactant with an alkaline agent and adjust the pH of the composition to the desired range. The commonly used alkaline agent is one or more of sodium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine, triethanolamine.

Cosolvent

The color-protecting liquid fabric detergent composition provided by the embodiment of the invention can also comprise a water-soluble cosolvent besides water. For improving the compatibility between the specific components and the composition and at the same time increasing the frost resistance of the composition. The cosolvent may be alcohol and alcohol ether with six or less carbons, and polyethylene glycol (PEG) or polypropylene glycol (PPG) with low molecular weight (200-600). Suitable examples include, but are not limited to, ethanol, glycerol, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, dipropylene glycol, diethylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, sorbitol, xylitol, PEG400, PPG400, and combinations of one or more thereof. The weight of the co-solvent is 0.5% to 30%, preferably 1% to 25%, more preferably 5% to 20% by weight of the total composition.

Washing assistant

The liquid detergent compositions to which the present invention relates may comprise detergency builders including bleach systems, anti-redeposition agents and optical brighteners. Wherein:

bleaching system

The liquid detergent compositions to which the present invention relates may comprise a bleach system. The bleaching system comprises hypohalite bleaching agent, peroxide bleaching agent. Peroxides typically comprise a source of hydrogen peroxide and a bleach activation system. Sources of hydrogen peroxide include, but are not limited to, perborates, persulfates, and mixtures thereof. The bleaching system may comprise a bleach activator for promoting rapid decomposition of peroxide at lower temperatures to generate oxygen selected from the group consisting of: tetraacetylethylenediamine, benzoyl caprolactam, 4-nitrobenzoyl caprolactam, 3-chlorobenzoyl caprolactam, benzoyloxybenzene sulfonate, nonanoyloxybenzene sulfonate, phenyl benzoate, decanoyloxybenzene sulfonate, benzoyl valerolactam, octanoyloxybenzene sulfonate and transition metal bleaching catalysts.

The liquid detergent composition of the present invention may further contain a reactive oxygen species stabilizer for adjusting the rate of generation of hydrogen peroxide by decomposition of the peroxide so that the local concentration of hydrogen peroxide is not too high, and examples thereof include polyfunctional organic phosphoric acids such as hydroxyethylidene diphosphate and ethylenediaminetermethylene phosphate. In some embodiments, the bleaching system is present at a level of from 0.01% to 30%, preferably from 0.01% to 20%, more preferably from 0.01% to 10% by weight of the total liquid detergent composition.

Anti-redeposition agent

The liquid detergent composition according to the present invention may contain an antiredeposition agent from the viewpoint of effectively improving the washing effect. The anti-redeposition agent includes, but is not limited to, the group consisting of: cellulose derivatives such as carboxymethyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose; homopolymers and copolymers of vinylpyrrolidone, such as linear polyvinylpyrrolidone, copolymers of vinylpyrrolidone and vinyl acetate, copolymers of vinylpyrrolidone and vinylimidazole; polycarboxylates, for example polyacrylates, polyacrylic polymaleic acid copolymers, acrylic acid-acrylate-sulfonate copolymers. The antiredeposition agent is present in the liquid detergent composition at a level of from 0.01% to 5%, preferably from 0.01% to 2%.

Fluorescent whitening agent

The use of optical brighteners in liquid detergent compositions is well known in the art and commercially available optical brighteners are abundant. Optical brighteners are present in the form of their alkali metal salts (mostly sodium salts). Preferred optical brighteners include, but are not limited to: distyrylbiphenyl compounds. A suitable example is 4,4' -bis (2-sodium sulfonate styryl) biphenyl, such as the product of the BASF company under the CBS-X brand. The fluorescent whitening agents are used in amounts of 0.01% to 2%, preferably 0.01% to 0.1% of the total composition.

The present invention relates to fabric liquid detergent compositions wherein the fluorescent whitening agent is present in the liquid detergent composition in an amount of from 0.01% to 2.00%, preferably from 0.05% to 1.00%, more preferably from 0.05% to 0.50% by weight.

Detergency testing method

Detergency in the present invention refers to the ability of a fabric detergent composition to remove various stains. The test is carried out according to the method of the national standard GB/T13174-2008. Three dirty cloths of carbon black, protein and sebum are adopted, and a WSD-3U fluorescence whiteness meter is used for measuring the whiteness W1 of the three dirty cloths before washing. Hard water with the hardness of 250ppm is prepared according to GB/T13174-2008 standard, and one-time washing is completed by adopting an RHLQ type vertical decontamination machine, wherein the addition amount of a detergent is 2g/L in a common type, and the concentration type is 0.7 g/L. Washing time is 20min, washing temperature is 30 ℃, stirring speed is 120r/min, the washed dirty cloth is rinsed and dried, whiteness W2 of the washed cloth piece is tested by a whiteness meter, and a whiteness difference delta W calculation method is as follows:

Δ W ═ W2-W1; wherein W2 is the whiteness after washing, and W1 is the whiteness before washing.

The detergency of the sample detergent is compared with that of the national standard detergent to calculate a P value,

P＝△W_{sample (I)}/△W_{Standard of merit}；△W_{Sample (I)}Is the difference of whiteness, delta W, of the soiled cloth before and after cleaning with the sample detergent_{Standard of merit}Is the whiteness difference of the dirty cloth before and after being cleaned by the national standard detergent.

Evaluation criteria for detergency

Higher P values indicate better detergency. If P is more than or equal to 1, the product is qualified, and if P is less than 1, the product is judged to be unqualified.

Color protection performance test method

The invention uses a horizontal decontamination machine, EMPA130 standard color cloth and national standard white cotton cloth to carry out color protection performance test. 4 pieces of 6 × 6cm coloured cloth and 2 pieces of 6 × 6cm white cotton cloth were cut, and the colour parameters of the pieces were measured using a colour difference meter and recorded as a standard. 300mL of 250ppm hard water, a certain amount of detergent (0.6 g of common detergent and 0.2g of concentrated detergent), the colored cloth and the white cloth are added into a decontamination tank. Washing at 30 deg.C and 120r/min for 30 min. And rinsing and drying the washed colored cloth and white cloth, and simultaneously sampling the washing solution.

Color parameters of the washed colored cloth and the white cloth are tested by using a color difference meter, and color difference values are calculated by contrasting the washed cloth pieces and are respectively recorded as delta E_{Color cloth}And Delta E_{White cloth}。

Using a color difference meter to test deionized water as a standard, testing the sampled washing liquid after washing, comparing with water to calculate a color difference value, and recording as delta E_{Liquid for treating urinary tract infection}。

According to the above method, the color difference of the white cloth and the cleaning solution before and after cleaning of the blank detergent without adding the modified polyethyleneimine and the cationic copolymer is recorded as delta E'_{Color cloth}，△E’_{White cloth}，△E’_{Liquid for treating urinary tract infection}。

Evaluation standard of color protection performance and influence degree on fabric appearance

△E_{Color cloth}Smaller values indicate less dye discoloration and polymer adhesion of the fabric pieces before and after washing of the colored fabrics, i.e., the detergent does not significantly affect the appearance of the fabric；△E_{White cloth}The smaller the numerical value is, the lighter the white cloth is dyed; delta E_{Liquid for treating urinary tract infection}The smaller the value, the lighter the discoloration of the color cloth.

The specific evaluation criteria are as follows in table 1:

2△E_{white cloth}<△E’_{White cloth}	Has obvious effect of preventing color cross talk
		△E_{White cloth}<△E’_{White cloth}<2△E_{White cloth}	Has weak effect of preventing color cross talk
△E_{White cloth}≥△E’_{White cloth}	Without cross color prevention effect
		△E_{Color cloth}≤△E’_{Color cloth}；△E_{Liquid for treating urinary tract infection}<△E’_{Liquid for treating urinary tract infection}	Has the effect of preventing fading without obviously influencing the appearance of the fabric
△E_{Color cloth}＞△E’_{Color cloth}；△E_{Liquid for treating urinary tract infection}<△E’_{Liquid for treating urinary tract infection}	Has the effect of preventing fading, but has obvious influence on the appearance of the fabric
		△E_{Color cloth}＞△E’_{Color cloth}；△E_{Liquid for treating urinary tract infection}≥△E’_{Liquid for treating urinary tract infection}	Has no anti-fading effect and has obvious influence on the appearance of the fabric
△E_{Color cloth}≤△E’_{Color cloth}；△E_{Liquid for treating urinary tract infection}≥△E’_{Liquid for treating urinary tract infection}	Has no anti-fading effect, but does not obviously influence the appearance of the fabric

Table 1 is a table of evaluation criteria of the bleaching condition of the colored cloth

When 2. delta. E is used according to the above evaluation criteria_{White cloth}<△E’_{White cloth}And Δ E_{Color cloth}≤△E’_{Color cloth}；△E_{Liquid for treating urinary tract infection}<△E’_{Liquid for treating urinary tract infection}And judging whether the color protection performance of the detergent and the influence degree on the fabric appearance are qualified or not, and judging whether the detergent is unqualified or not.

Stability test method and evaluation standard

High temperature stability: after bottling and sealing the composition, placing at 45 + -2 deg.C, maintaining at constant temperature for one month, recovering to room temperature of 25 + -5 deg.C, and determining that the stability at high temperature is qualified, otherwise determining that the stability is not qualified.

Stability at Low temperature: after bottling and sealing the composition, placing at 0 + -2 deg.C for one month, directly observing, and determining that the low temperature stability is qualified or not by precipitation or delamination.

Stability at Normal temperature: after the composition is bottled and sealed, the mixture is placed at 25 +/-5 ℃ for one month, no precipitate is separated out or layered, the stability at normal temperature is qualified, and otherwise, the stability is unqualified.

Stability of aging Properties: after the composition is bottled and sealed, the bottled and sealed composition is placed at 37 +/-2 ℃ for one month, no precipitate is separated out or layered, the evaluation of the color protection performance and the influence degree on the appearance of the fabric can be qualified, the aging stability is qualified, and otherwise, the aging stability is unqualified.

Performance test experiment

The stable color-protecting liquid detergent compositions of the present invention are prepared by various methods well known to those skilled in the art. The formulation of the composition may be carried out by conventional means, and the appropriate processing temperature and processing time will be selected with reference to the state and effect of the components in solution, and the stability of the components.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following examples are intended to further describe and demonstrate embodiments within the scope of the present invention. The examples are therefore to be understood as merely illustrative of the invention in more detail and not as limiting the content of the invention in any way.

In the following examples, all amounts are by weight unless otherwise indicated, and the amounts of the listed ingredients are converted to active material amounts.

In the examples, the following abbreviations will be used and have the indicated functions.

Liquid caustic soda (32%): sodium hydroxide water solution containing 32% of sodium hydroxide by mass, neutralizing fatty acid and saponifying to prepare fatty acid salt and/or neutralizing LAS, alkali agent.

And (3) LAS: sodium linear alkyl benzene sulfonate having a linear alkyl group of 10 to 13 carbon atoms, and an anionic surfactant.

AES: ethoxylated fatty alcohol sulfate having 12 to 14 carbon atoms of fatty alcohol and an average degree of ethoxylation of 2, and an anionic surfactant.

Performance testing of conventional color-protecting detergent compositions

In order to facilitate comparison of the performance of liquid detergents of different compositions, general type color-protecting detergent compositions comparative examples 1 to 7 were prepared using the same preparation method, and the components of each comparative example are shown in Table 2 below:

TABLE 2 color-protecting detergent compositions of different Components comparative examples 1 to 7

As can be seen from table 2, comparative example 1 is a liquid fabric detergent containing no modified polyethyleneimine and no cationic polymer, comparative example 2 is a liquid fabric detergent containing no cationic polymer, comparative example 3 is a liquid fabric detergent containing no modified polyethyleneimine, and comparative examples 4 to 7 are liquid fabric detergents containing modified polyethyleneimine and a cationic polymer, wherein the ratio of the modified polyethyleneimine to the cationic polymer is different.

The prepared comparative examples 1 to 7 were tested according to the color protection performance test method and evaluated according to the evaluation criteria table of the discoloring condition of the colored cloth of table 1, and the results are shown in table 3:

TABLE 3 examination of the effects of color protection and textile appearance

As can be seen from Table 3, comparative examples 4 to 7 of the liquid fabric detergents containing the modified polyethyleneimine and the cationic polymer were satisfactory in color-protecting properties; comparative example 2 of the liquid fabric detergent without cationic polymer and comparative example 3 of the liquid fabric detergent without modified polyethyleneimine do not meet the color protection performance.

The test and evaluation were performed according to the detergency test method, and the test results are shown in table 4:

table 4 detergency test results

As can be seen from table 4, comparative example 3, which contained no modified polyethyleneimine, had unsatisfactory detergency performance, and the remaining comparative examples all had satisfactory detergency.

The test and evaluation were performed according to the stability test method and evaluation criteria, and the test results are shown in tables 5 and 6:

table 5 stability test results

Comparative example 1

Comparative example 2

Comparative example 3

Comparative example 4

Comparative example 5

Comparative example 6

Comparative example 7

High temperature stability

Qualified

Fail to be qualified

Qualified

Stability at Low temperature

Qualified

Fail to be qualified

Qualified

Stability at Normal temperature

Qualified

Fail to be qualified

Qualified

TABLE 6 stability of aging Properties

As can be seen from tables 2 to 6, in the composition described above, comparative example 2, in which only the modified polyethyleneimine is added, can achieve a significant cross-color prevention effect, but at this time, the color removal of the colored cloth is severe, and the appearance of the fabric is significantly affected. Also, comparative example 3, in which only the cationic polymer was added, required a large amount of addition in order to achieve a good anti-cross-color effect, and in this case, the color of the colored cloth was changed due to adsorption of the excessive polymer, although the anti-color-fading property of the detergent was more prominent. Comparative examples 4-7 show that acceptable color protection can be achieved by compounding two polymers in different formulations, and that the fabric appearance is not significantly affected.

In addition, the results of the stain removal test of the composition according to the national stain removal method show that comparative example 2 shows that the modified polyethyleneimine alone does not adversely affect the detergency of the detergent. Comparative example 3 presents a significant detergency reduction problem, and the remaining samples are in the preferred range, and the formulation of the modified polyethyleneimine with the cationic polymer in the detergent does not adversely affect the detergency performance of the detergent.

In the stability test of high temperature, low temperature and normal temperature, the turbidity appears due to the influence of a large amount of cationic copolymers in the comparative example 3 on the stability of the detergent, and the problem of precipitation is also generated through long-term stability test. And in the comparative examples 4 to 7, the compound of the two polymers reduces the use amount of the polymers, ensures the color protection performance of the composition and improves the integral stability of the detergent.

Further aging property stability examination shows that the color cross-discoloration prevention and color fading prevention properties of some samples in comparative examples 4-7 are reduced to a certain extent after aging, and particularly, in comparative example 4, the sample added with 0.6% of modified polyethyleneimine and 0.015% of cationic copolymer has no stability problem in appearance, but the properties are reduced to an unqualified range after aging. And after aging, the comparative examples 5 to 7 still can achieve a more balanced effect in the aspects of color cross-color prevention and color fading prevention, and the stability is qualified.

In combination with the above results, comparative examples 5 to 7 were compositions which were acceptable in terms of detergency, stability, color protection and fabric appearance impact.

Performance testing of concentrated color-protecting detergent compositions

Comparative examples 8 to 10 of concentrated color-protecting detergents were prepared by the same preparation method, and the performance effects of the concentrated detergents of different components were compared, each component of comparative examples 8 to 10 is shown in table 7, the results of tests and evaluations according to the color-protecting performance test method are shown in table 8, the results of detergency tests are shown in table 9, and the results of stability tests are shown in tables 10 and 11:

TABLE 7 color-protecting detergent compositions comparative examples 8-10 component tables

	Comparative example 8	Comparative example 9	Comparative example 10
				Components	Content (%)	Content (%)	Content (%)
Glycerol	6	0	0
				Propylene glycol	16	5	5
Monoethanolamine	4.8	3.7	1.6
				Fatty acids	5	4	4
AES	15	10	8
				LAS	20	15	0
Straight chain alkyl polyoxyethylene ether	10	8	25
				Branched alkyl polyoxyethylene ether	10	5	15
Modified polyethyleneimine	3	2	3
				Cationic copolymers	0.2	0.1	0.5
Water, enzyme, antiseptic, essence and antioxidant	Balance of	Balance of	Balance of

TABLE 8 results of investigation of color protection and fabric appearance impact

	Comparative example 1	Comparative example 8	Comparative example 9	Comparative example 10
					△E_{Color cloth}	1.34	1.03	0.98	1.26
△E_{White cloth}	19.45	5.11	4.22	3.87
					△E_{Liquid for treating urinary tract infection}	2.25	2.04	1.97	0.64
Evaluation results	Blank space	Qualified	Qualified	Qualified

TABLE 9 detergency test investigation results

TABLE 10 stability test results

	Comparative example 8	Comparative example 9	Comparative example 10
				High temperature stability	Qualified	Qualified	Qualified
Stability at Low temperature	Qualified	Qualified	Qualified
				Stability at Normal temperature	Qualified	Qualified	Qualified

TABLE 11 stability of aging Properties

	Comparative example 1	Comparative example 8	Comparative example 9	Comparative example 10
					△E_{Color cloth}	1.29	1.09	1.04	1.16
△E_{White cloth}	18.79	5.00	4.67	4.83
					△E_{Liquid for treating urinary tract infection}	2.36	2.13	1.86	0.87
Evaluation results	Blank space	Qualified	Qualified	Qualified

From tables 8 to 11, it can be seen that the performance tests of the concentrated detergent are also performed, and within the preferred range provided by the embodiment of the present invention, the color-protecting liquid fabric detergent composition provided by the present invention has good stability, good stain-removing and color-protecting performance, and no obvious influence on the fabric appearance, and can effectively protect the clothes.

In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. The color-protecting liquid fabric detergent composition is characterized by comprising the following components in parts by weight:

5-70 parts of a surfactant system;

0.1-5 parts of modified polyethyleneimine;

0.01-1 part of cationic polymer;

0.1-30 parts of an additive;

the cationic polymer has

Wherein a and b are positive integers; and is

Is a cationic structural unit and is characterized in that,

at least one selected from the following structures:

the ratio of the modified polyethyleneimine to the cationic polymer is 30:1 to 3: 1;

the modified polyethyleneimine is ethoxy and/or propoxy modified polyethyleneimine;

the average degree of ethoxylation in the modified polyethyleneimine is from 2 to 50;

cationic structural units in the cationic polymer

Selected from compounds corresponding to the following general formula (1):

x is selected from OH, Cl, Br or CH₃OSO₃At least one of;

or, a cationic structural unit in the cationic polymer

Selected from compounds corresponding to the following general formula (2):

wherein Y is selected from O or NR³At least one of;

R³is selected from H or CH₃；

R⁴Is selected from C_nH_2n+1、C_mH_2m-1、(CH₂CH₂O)_vH. Phenyl or naphthaleneAt least one of the groups, n is 0-4, m is 5-8, v is 1-3;

x is selected from OH, Cl, Br or CH₃OSO₃At least one of (1).

2. The color-protecting liquid fabric detergent composition according to claim 1, wherein the modified polyethyleneimine is an ethoxy-modified polyethyleneimine.

3. The color-protecting liquid fabric detergent composition according to claim 2, wherein the weight average molecular weight of the main chain in the modified polyethyleneimine is 300 to 8000.

4. The color-protecting liquid fabric detergent composition of claim 1, wherein the cationic polymer comprises from 15% to 50% by weight of cationic building blocks, based on the total weight of the cationic polymer.

5. The color-protecting liquid fabric detergent composition of claim 1, wherein the additive comprises at least one of an enzyme preparation, an alkaline agent, a viscosity modifier, a co-solvent, a pH stabilizer, a preservative, a colorant, a detergency builder, a color stabilizer, and a perfume.